CN108682824A - A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery - Google Patents

A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery Download PDF

Info

Publication number
CN108682824A
CN108682824A CN201810551396.7A CN201810551396A CN108682824A CN 108682824 A CN108682824 A CN 108682824A CN 201810551396 A CN201810551396 A CN 201810551396A CN 108682824 A CN108682824 A CN 108682824A
Authority
CN
China
Prior art keywords
sio
active material
based active
composite negative
unsaturated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810551396.7A
Other languages
Chinese (zh)
Inventor
邓志强
庞春雷
任建国
黄友元
岳敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen BTR New Energy Materials Co Ltd
Original Assignee
Shenzhen BTR New Energy Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen BTR New Energy Materials Co Ltd filed Critical Shenzhen BTR New Energy Materials Co Ltd
Priority to CN201810551396.7A priority Critical patent/CN108682824A/en
Publication of CN108682824A publication Critical patent/CN108682824A/en
Priority to EP19811058.7A priority patent/EP3758114A4/en
Priority to JP2021508042A priority patent/JP7095176B2/en
Priority to KR1020207032531A priority patent/KR102558278B1/en
Priority to US17/059,445 priority patent/US11909035B2/en
Priority to PCT/CN2019/075333 priority patent/WO2019227972A1/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery.The composite negative pole material includes SiOxBased active material and it is coated on the SiOxThe makrolon clad on based active material surface.The method includes：1) monomer solution of unsaturated carbon acid ester is prepared；2) so that monomer is polymerize under the conditions of existing for polymerization catalyst, obtain polymer solution；3) SiO is added into polymer solutionxBased active material, water and polyalcohol catalyst continue polymerization and to SiOxBased active material is coated, and composite negative pole material is obtained.The composite negative pole material of the present invention can inherently participate in the formation of SEI films, form more stable SEI films, improve SEI films to avoid destroying and rebuilding repeatedly, the final cycle performance for improving lithium ion battery extends its service life.

Description

A kind of composite negative electrode material of lithium ion battery, preparation method and in lithium-ion electric Purposes in pond
Technical field
The present invention relates to field of lithium ion battery, it is related to a kind of composite negative electrode material of lithium ion battery, preparation method And the purposes in lithium ion battery.
Background technology
In order to improve the energy density of lithium ion battery, in the latest 20 years, people also open around the exploitation of high power capacity cathode A large amount of pilot study is opened up.Silicon is because with highest theoretical specific capacity and abundance, cheap, environmental-friendly The features such as and as current lithium ion battery negative material research hotspot.But due to serious bulk effect, silica-base material Cycle performance it is excessively poor, cannot be satisfied commercial applications.SiOxWhile material has high power capacity, have more excellent than elemental silicon Cycle performance more, is widely paid close attention to and is studied.But its cycle performance still has larger gap compared to graphite, it is difficult to adapt to Commercialization demand.Therefore, it is still affiliated neck to develop the SiOx base negative materials that a kind of cycle performance is excellent, Volumetric expansion is low The technical barrier in domain.
The destruction repeatedly and reconstruction of SEI films are to lead to SiOxOne of the principal element of sill stable circulation sex chromosome mosaicism, has In consideration of it, it is necessary to provide a kind of novel composite negative pole material, the formation of SEI films is inherently participated in, it is more steady to be formed Fixed SEI films improve SEI films to avoid destroying and rebuilding repeatedly, and the final cycle performance for improving lithium ion battery, extending it makes Use the service life.
Invention content
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of composite negative pole material, its Preparation method and the purposes in lithium ion battery.The composite negative pole material of the present invention can inherently participate in the formation of SEI films, More stable SEI films are formed, improve SEI films to avoid destruction repeatedly and are rebuild, the final cyclicity for improving lithium ion battery Can, extend its service life.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of composite negative electrode material of lithium ion battery, the composite negative pole material includes SiOxBased active material and it is coated on the SiOxThe makrolon clad on based active material surface.
In composite negative pole material of the present invention, makrolon is coated on SiO securelyxThe surface of based active material, Protect SiOxWhile based active material, in SiOxIn based active material charge and discharge process, the formation of SEI films is participated in, increases SEI The polycarbonate component of high molecular weight in film improves the toughness of SEI films, improves the stability of SEI films to avoid destroying repeatedly With reconstruction, the final cycle performance for improving battery.
Makrolon of the present invention cannot by other resin replacements because, makrolon can match existing electrolyte at Point, the reaction for forming SEI films is participated in, and other kinds of resin is then unable to reach this effect.
As the optimal technical scheme of composite negative pole material of the present invention, the SiOxThe grain size of based active material exists 0.5 μm -100 μm, such as 0.5 μm, 1 μm, 3 μm, 6 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 45 μm, 50 μm, 60 μm, 70 μ M, 80 μm, 90 μm or 100 μm etc., preferably 5 μm -50 μm.
Preferably, the SiOxBased active material is SiOx、SiOx/ C or SiOxAny one in/M or at least two Combination, wherein M is any one or at least two in alkali metal, alkaline-earth metal, alkali metal oxide or alkaline earth oxide The combination of kind, 0 x≤2 ＜.
" SiO of the present inventionx/ C " refers to SiOxWith the compound of C, " SiOx/ M " refers to SiOxWith the compound of M.
Preferably, the thickness of the makrolon clad is in 10nm-100nm, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 85nm or 100nm etc., if thickness is less than 10nm, clad is easily broken；If thickness More than 100nm, the electronics for influencing material is conducted, preferably 20nm-50nm.
Preferably, with the SiOxThe gross mass of based active material is 100% meter, the quality of the makrolon clad Percentage is 0-10% and does not include 0, such as 0.5%, 1%, 2%, 2.5%, 3%, 4%, 6%, 6.5%, 7%, 8%, 9% Or 10% etc., preferably 3%-7% can be to SiO in this preferred scope 3%-7%xBased active material forms more suitable thickness Clad, and preferably promote chemical property.
Preferably, the makrolon clad is polymerized by unsaturated carbon acid ester, and the unsaturated carbon acid ester has Following structural formula：
Wherein, R1And R2It is at least one be the unsaturated group containing carbon-carbon double bond or three key, moreover, when only there are one For unsaturated group containing carbon-carbon double bond or three key when, another is any one in H, alkyl or aromatic radical.
In the present invention, the SiOxBased active material and makrolon clad are connected directly；Or the SiOxBase activity It is connected by unsaturated silane coupling agent between material and makrolon clad.
The preferred structure of composite negative pole material of the present invention is：SiOxBetween based active material and makrolon clad It is connected by unsaturated silane coupling agent, to form composite negative pole material.By the connection of silane coupling agent, poly- carbonic acid can be made Ester clad is more stablized, securely, to keep the SEI that makrolon participates in being formed more difficult from material surface disengaging, finally Cycle performance of battery is more excellent.
Preferably, the unsaturated silane coupling agent has the following structure formula：
Wherein, R3For the alkyl with 1 to 6 carbon atoms, R4For the unsaturated group containing carbon-carbon double bond or three key.
Preferably, with the SiOxThe gross mass of based active material is 100% meter, the matter of the unsaturated silane coupling agent Amount percentage is 0-5%, such as 0,0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.2%, 3.6%, 4% or 5% etc., it is excellent It is selected as 1%-3%." mass percent 0 " refers to without containing unsaturated silane coupling agent.
Second aspect, the present invention provide the preparation method of composite negative pole material as described in relation to the first aspect, the method packet Include following steps：
(1) monomer solution of unsaturated carbon acid ester is prepared；
(2) existing for polymerization catalyst so that monomer is polymerize under the conditions of, obtain polymer solution；
(3) SiO is added into polymer solutionxBased active material, water and polyalcohol catalyst continue polymerization simultaneously To SiOxBased active material is coated, and composite negative pole material is obtained.
Unsaturated carbon acid ester is carried out prepolymerization by the method for the present invention first, then disperses SiO theretoxBased active material, Unsaturated carbon acid ester is while polymerization in SiOxBased active material surface carries out in-stiu coating so that last gained SiOxBase is lived Property material cladding last layer high molecular weight makrolon.
Moreover, the preparation method of the present invention is simple for process, effective, it is of low cost, it is easy to accomplish industrialization and production process It is environmentally protective.
As the optimal technical scheme of the method for the invention, the method further include be covered to complete in step (3) it is laggard The step of row solid is separated and dried.
The method that the present invention uses solid separation is not construed as limiting, such as can is natural filtration, be filtered under diminished pressure or centrifuge Deng.
Preferably, the temperature of the drying be 80 DEG C -150 DEG C, such as 80 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc..
Preferably, the time of the drying is 2h-12h, such as 2h, 4h, 6h, 7h, 8h, 10h, 11h or 12h etc..
As the optimal technical scheme of the method for the invention, step (1) is：Unsaturated carbon acid ester is dissolved in solvent In；Or unsaturated carbon acid ester and unsaturated silane coupling agent are dissolved in solvent.
It is highly preferred that step (1) is：Unsaturated carbon acid ester and unsaturated silane coupling agent are dissolved in solvent.This is excellent Under the conditions of choosing, in the polymerization process of unsaturated carbon acid ester, unsaturated silane coupling agent is added and is copolymerized, by silane coupled Agent respectively with makrolon, SiOxCovalent key connection between based active material, makes makrolon be coated on SiO more securelyx Based active material surface, to preferably play the role of protection activity material.
Preferably, in step (1), the solvent is water, methanol, ethyl alcohol, polypyrrole alkanone, isopropanol, tetrahydrofuran, second Any one in acetoacetic ester, n,N-dimethylacetamide, n,N-Dimethylformamide, n-hexane or halogenated hydrocarbons or at least two Combination, preferably in ethyl alcohol, polypyrrole alkanone, isopropanol, tetrahydrofuran, ethyl acetate or n,N-Dimethylformamide appoint It anticipates a kind of or at least two combinations.
Preferably, in step (1), a concentration of 5wt%-10wt% of unsaturated carbon acid ester in the monomer solution, such as 5wt%, 6wt%, 7wt%, 8wt%, 8.5wt%, 9wt% or 10wt% etc..
Preferably, in step (1), the mass ratio of the unsaturated carbon acid ester and unsaturated silane coupling agent is 2:1-7:1, Such as 2:1、3:1、4:1、5:1、6:1、6.5:1 or 7:1 etc..
Preferably, step (2) and step (3) described polyalcohol catalyst are independently selected from potassium peroxydisulfate, sodium peroxydisulfate, mistake Any one in ammonium sulfate, dibenzoyl peroxide or azodiisobutyronitrile.
Preferably, step (2) and the total polymerization time of step (3) are 2h-10h, for example, 2h, 3.5h, 4.5h, 6h, 8h or 10h etc..
Preferably, step (2) and the temperature of step (3) described polymerization be independently at 50 DEG C -100 DEG C, for example, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 85 DEG C, 90 DEG C or 100 DEG C etc..
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) unsaturated carbon acid ester and unsaturated silane coupling agent are dissolved in solvent, to which unsaturated carbon be prepared The monomer solution of acid esters；
(2) existing for polymerization catalyst so that monomer is polymerize at 50 DEG C -100 DEG C under the conditions of, obtain polymer solution；
(3) SiO is added into polymer solutionxBased active material, water and polyalcohol catalyst continue at 50 DEG C -100 DEG C carry out polymerization and to SiOxBased active material is coated；
(4) solid detaches and in 80 DEG C -150 DEG C dry 2h-12h, obtains composite negative pole material.
The third aspect, the present invention provide a kind of cathode, and the cathode includes the composite negative pole material described in first aspect.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes negative described in the third aspect Pole.
Compared with the prior art, the present invention has the advantages that：
(1) in the composite negative pole material with makrolon cladding of the invention, makrolon is coated on SiO securelyx Based active material surface, while protecting SiOx based active materials, in SiOxIn the charge and discharge process of based active material, participate in The formation of SEI films increases the polycarbonate component of high molecular weight in SEI films, improves the toughness of SEI films, improves the steady of SEI films It is qualitative to avoid destroying and rebuild repeatedly, the final cycle performance for improving battery.
The composite negative pole material of the present invention is due to the introducing with suitable makrolon clad, as negative material application Excellent electrochemistry cycle and low expansion energy are shown in lithium ion battery, the service life of lithium ion battery can be extended.
(2) preparation method raw material of the present invention is cheap, and simple for process, mild condition is not high to equipment requirement, at low cost.Together When, it is generated without poisonous and hazardous intermediate product in preparation process, production process is environmentally protective, is easy to mass produce.
Description of the drawings
Fig. 1 is 50 weeks cycle performance test result comparison diagrams of SI-1, SI-2 and Ref-1；
Fig. 2 a and Fig. 2 b are respectively the SEM figures of the negative material of SI-1 and SI-2.
Specific implementation mode
In order to more clearly from illustrate the goal of the invention of the present invention, technical solution and technique effect, below in conjunction with specific reality Applying example and attached drawing, the present invention is described in detail.
Embodiment 1
5g vinylene carbonates are dissolved in 100ml ethyl acetate, after being warming up to 70 DEG C, 0.2g ammonium persulfates are added, After being stirred to react 1 hour, 100g SiO are addedx(x=1), the water of 0.2g ammonium persulfates and 5g reacts 4h postcoolings, filters and divides Solid matter is separated out, is subsequently placed in 80 DEG C of drying box and is heat-treated 8h, it is cooling to obtain accordingly with makrolon cladding Composite negative pole material.
Embodiment 2
5g vinylene carbonates and 2g vinyltrimethoxysilanes are dissolved in 100ml ethyl acetate, are warming up to 70 After DEG C, 0.2g ammonium persulfates are added, after being stirred to react 1 hour, 100g SiO are addedx(x=1), 0.2g ammonium persulfates and 5g Water reacts 4h postcoolings, and suction filtration isolates solid matter, is subsequently placed in 100 DEG C of drying box and is heat-treated 8h, and cooling obtains phase The composite negative pole material with makrolon cladding answered.
Embodiment 3
7g vinyl ethylene carbonates are dissolved in 100ml n,N-Dimethylformamide, after being warming up to 85 DEG C, are added After being stirred to react 2 hours, 100g SiO are added in 0.2g sodium peroxydisulfatesx(x=1.5), 2g water and 0.2g potassium peroxydisulfates react 6h Postcooling, suction filtration isolate solid matter, are subsequently placed in 80 DEG C of drying box and are heat-treated 12h, and cooling is had accordingly The composite negative pole material of makrolon cladding.
Embodiment 4
7g vinyl ethylene carbonates and 1g vinyltriethoxysilane are dissolved in 100ml N, N- dimethyl formyls In amine, after being warming up to 100 DEG C, 0.2g dibenzoyl peroxides are added, after being stirred to react 1 hour, 100g SiO are addedx/ C (x= 1), 10g water and 0.3g dibenzoyl peroxides, react 7h postcoolings, and suction filtration isolates solid matter, is subsequently placed in 120 DEG C 3h, the cooling composite negative pole material obtained accordingly with makrolon cladding are heat-treated in drying box.
Embodiment 5
10g acrylic benzol carbonates are dissolved in 100ml polypyrrole alkanones, after being warming up to 65 DEG C, 0.5g mistakes are added After being stirred to react 3.5 hours, 100g SiO are added in potassium sulfatex/ Mg, 2g water (x=1.5) and 0.2g potassium peroxydisulfates react 4.5h Postcooling is filtered under diminished pressure out solid matter, is subsequently placed in 135 DEG C of drying box and is heat-treated 4.5h, and cooling is had accordingly There is the composite negative pole material that makrolon coats.
Test：
Negative material prepared by embodiment 1-5 is applied in lithium ion battery, number is respectively SI-1, SI-2, SI- 3, SI-4 and SI-5.As reference group, SiO and SiO is used respectivelyx/ C (x=1.0) prepares lithium-ion electric as negative material Pond, number are Ref-1 and Ref-2.Use the SiO for the SiO and epoxy resin cladding that phenolic resin coats as cathode material respectively Material prepares lithium ion battery, number Ref-3, Ref-4.
By prepared by above-described embodiment 1-5 negative material and the corresponding negative materials of Ref-1 to Ref-4 respectively with carboxylic Sodium carboxymethylcellulose pyce, butadiene-styrene rubber and electrically conductive graphite (KS-6) and carbon black (SP) proportionally 92:2:2:2:2 configuration slurries, Uniformly cathode pole piece is made with drying on copper foil in coating, button cell is assembled into argon gas atmosphere glove box, diaphragm used is Microporous polypropylene membrane, (solvent is ethylene carbonate, methyl ethyl carbonate and carbonic acid to the lithium hexafluoro phosphate that electrolyte used is 1mol/L The mixed liquor of dimethyl ester), used is metal lithium sheet to electrode.
Loop test is carried out to above-mentioned battery, test equipment is blue electric battery test system CT2001C, test temperature 25 DEG C, voltage range is 0.005V~1.5V, and charge and discharge 50 weeks are carried out with the current density of 1C.Capacity is calculated after loop test to keep Rate, and lithium ion battery is disassembled, measure the thickness of cathode pole piece.Wherein, 50 weeks circulation volume conservation rate=50th week cycles are put Capacitance/the first week discharge capacity * 100%, the results are shown in Table 1；50 weeks expansion rates of cathode pole piece thickness=(recycle for the 50th week The thickness of the uncharged pole piece of thickness-afterwards)/uncharged pole piece thickness * 100%, the results are shown in Table 1.
Fig. 1 is 50 weeks cycle performance test result comparison diagrams of SI-1, SI-2 and Ref-1.
Fig. 2 a and Fig. 2 b are respectively the SEM figures of the negative material of SI-1 and SI-2.
Table 1：The 50 weeks circulation volume conservation rates and pole piece expansion rate of each battery
By the test result of table 1 it can be found that using SiO of the inventionxBattery of the sill as negative electrode active material, 50 weeks circulation volume conservation rates and pole piece expansion rate all significantly improve, and reference group is not lived using cathode prepared by the present invention Property material, effect are inferior to each embodiment.Wherein, reference group Ref-1, Ref-3 and Ref-4 and the SiO in embodiment SI-1xBase Material is only that surface coating layer is different, SiOxThere is the cycle performance of battery in the SI-1 of makrolon clad on sill surface It is substantially better than these three reference groups.The improvement of cycle performance of battery has benefited from the improvement result of makrolon clad, and Ref-3 It is because of phenolic resin with the cycle performance for coating or even deteriorating battery of phenolic resin, epoxy resin in Ref-4 reference groups SiO can not be participated in as makrolon with epoxy resinxThe SEI films on sill surface build to improve the stabilization of SEI Property, and their presence affects electronics conduction and the formation of material surface SEI films of material, so that deteriorating battery Cycle performance.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field Technical staff is it will be clearly understood that embodiment described in this specification is intended to the explanation present invention, the specific substance being previously mentioned, recipe ratio Example and reaction condition only the above-mentioned substance being previously mentioned of the invention, formula rate and reaction condition concrete embodiment simultaneously It is non-that the present invention is further limited, it is every to be become using equivalent structure made by description of the invention and accompanying drawing content or equivalent process It changes, is applied directly or indirectly in other relevant technical fields, and all belongs to the scope of the present invention.

Claims (10)

1. a kind of composite negative electrode material of lithium ion battery, which is characterized in that the composite negative pole material includes SiOxBase activity material Expect and be coated on the SiOxThe makrolon clad on based active material surface.
2. composite negative pole material according to claim 1, which is characterized in that the SiOxThe grain size of based active material is 0.5 μm -100 μm, preferably 5 μm -50 μm；
Preferably, the SiOxBased active material is SiOx、SiOx/ C or SiOxIn/M any one or at least two combination, Wherein, M is any one in alkali metal, alkaline-earth metal, alkali metal oxide or alkaline earth oxide or at least two Combination, 0 x≤2 ＜.
3. composite negative pole material according to claim 1 or 2, which is characterized in that the thickness of the makrolon clad In 10nm-100nm, preferably 20nm-50nm；
Preferably, with the SiOxThe gross mass of based active material is 100% meter, the quality percentage of the makrolon clad Than for 0-10% and do not include 0, preferably 3%-7%；
Preferably, the makrolon clad is polymerized by unsaturated carbon acid ester, and the unsaturated carbon acid ester has as follows Structural formula：
Wherein, R1And R2It is at least one be the unsaturated group containing carbon-carbon double bond or three key, moreover, when only there are one for containing When having the unsaturated group of carbon-carbon double bond or three key, another is any one in H, alkyl or aromatic radical.
4. according to claim 1-3 any one of them composite negative pole materials, which is characterized in that the SiOxBased active material and Makrolon clad is connected directly；Or the SiOxPass through unsaturated silicon between based active material and makrolon clad Alkane coupling agent is connected；
Preferably, the unsaturated silane coupling agent has the following structure formula：
Wherein, R3For the alkyl with 1 to 6 carbon atoms, R4For the unsaturated group containing carbon-carbon double bond or three key；
Preferably, with the SiOxThe gross mass of based active material is 100% meter, the quality hundred of the unsaturated silane coupling agent Divide than being 0-5%, preferably 1%-3%.
5. the preparation method of composite negative pole material according to any one of claims 1-4, which is characterized in that the method includes Following steps：
(1) monomer solution of unsaturated carbon acid ester is prepared；
(2) existing for polymerization catalyst so that monomer is polymerize under the conditions of, obtain polymer solution；
(3) SiO is added into polymer solutionxBased active material, water and polyalcohol catalyst, continue polymerization and it is right SiOxBased active material is coated, and composite negative pole material is obtained.
6. according to the method described in claim 5, it is characterized in that, the method further include be covered to complete in step (3) it is laggard The step of row solid is separated and dried；
Preferably, the method that solid separation uses includes natural filtration, be filtered under diminished pressure or centrifuge in any one；
Preferably, the temperature of the drying is 80 DEG C -150 DEG C；
Preferably, the time of the drying is 2h-12h.
7. method according to claim 5 or 6, which is characterized in that step (1) is：Unsaturated carbon acid ester is dissolved in molten In agent；Or unsaturated carbon acid ester and unsaturated silane coupling agent are dissolved in solvent；
Preferably, in step (1), the solvent is water, methanol, ethyl alcohol, polypyrrole alkanone, isopropanol, tetrahydrofuran, acetic acid second In ester, n,N-dimethylacetamide, n,N-Dimethylformamide, n-hexane or halogenated hydrocarbons any one or at least two group It closes, it is preferably any one in ethyl alcohol, polypyrrole alkanone, isopropanol, tetrahydrofuran, ethyl acetate or n,N-Dimethylformamide Kind or at least two combination；
Preferably, in step (1), a concentration of 5wt%-10wt% of unsaturated carbon acid ester in the monomer solution；
Preferably, in step (1), the mass ratio of the unsaturated carbon acid ester and unsaturated silane coupling agent is 2:1-7:1；
Preferably, step (2) and step (3) described polyalcohol catalyst are independently selected from potassium peroxydisulfate, sodium peroxydisulfate, persulfuric acid Any one in ammonium, dibenzoyl peroxide or azodiisobutyronitrile；
Preferably, step (2) and the total polymerization time of step (3) are 2h-10h；
Preferably, step (2) and the temperature of step (3) described polymerization are independently at 50 DEG C -100 DEG C.
8. according to claim 5-7 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) unsaturated carbon acid ester and unsaturated silane coupling agent are dissolved in solvent, to which unsaturated carbon acid ester be prepared Monomer solution；
(2) existing for polymerization catalyst so that monomer is polymerize at 50 DEG C -100 DEG C under the conditions of, obtain polymer solution；
(3) SiO is added into polymer solutionxBased active material, water and polyalcohol catalyst, continue 50 DEG C -100 DEG C into Row polymerize and to SiOxBased active material is coated；
(4) solid detaches and in 80 DEG C -150 DEG C dry 2h-12h, obtains composite negative pole material.
9. a kind of cathode, which is characterized in that the cathode includes claim 1-4 any one of them composite negative pole materials.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes the cathode described in claim 9.
CN201810551396.7A 2018-05-31 2018-05-31 A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery Pending CN108682824A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201810551396.7A CN108682824A (en) 2018-05-31 2018-05-31 A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery
EP19811058.7A EP3758114A4 (en) 2018-05-31 2019-02-18 Composite negative electrode material for lithium ion battery, preparation method therefor and use thereof in lithium ion battery
JP2021508042A JP7095176B2 (en) 2018-05-31 2019-02-18 Composite negative electrode material for lithium-ion batteries, its manufacturing method, and applications for lithium-ion batteries
KR1020207032531A KR102558278B1 (en) 2018-05-31 2019-02-18 Composite anode material for lithium ion battery, manufacturing method thereof, and use in lithium ion battery
US17/059,445 US11909035B2 (en) 2018-05-31 2019-02-18 Composite negative electrode material for lithium ion battery, preparation method thereof, and use thereof in lithium ion battery
PCT/CN2019/075333 WO2019227972A1 (en) 2018-05-31 2019-02-18 Composite negative electrode material for lithium ion battery, preparation method therefor and use thereof in lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810551396.7A CN108682824A (en) 2018-05-31 2018-05-31 A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery

Publications (1)

Publication Number Publication Date
CN108682824A true CN108682824A (en) 2018-10-19

Family

ID=63809533

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810551396.7A Pending CN108682824A (en) 2018-05-31 2018-05-31 A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery

Country Status (6)

Country Link
US (1) US11909035B2 (en)
EP (1) EP3758114A4 (en)
JP (1) JP7095176B2 (en)
KR (1) KR102558278B1 (en)
CN (1) CN108682824A (en)
WO (1) WO2019227972A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109494360A (en) * 2018-10-26 2019-03-19 合肥国轩高科动力能源有限公司 A kind of oxidation Asia silicon composite and preparation method thereof
WO2019227972A1 (en) * 2018-05-31 2019-12-05 深圳市贝特瑞新能源材料股份有限公司 Composite negative electrode material for lithium ion battery, preparation method therefor and use thereof in lithium ion battery
CN112259736A (en) * 2020-10-27 2021-01-22 成都新柯力化工科技有限公司 Lithium titanate negative electrode for relieving flatulence of lithium battery and preparation method
CN112574659A (en) * 2020-12-11 2021-03-30 中国科学院青岛生物能源与过程研究所 Electrode plate protective layer of lithium secondary battery and preparation method thereof
CN112968151A (en) * 2019-12-12 2021-06-15 郑州宇通集团有限公司 Negative electrode active material, preparation method thereof and lithium ion battery

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113659218A (en) * 2021-08-12 2021-11-16 湖南金硅科技有限公司 High-capacity and high-magnification cylindrical lithium ion battery and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105359309A (en) * 2013-07-08 2016-02-24 三洋化成工业株式会社 Resin for coating lithium-ion-battery active material, resin composition for coating lithium-ion-battery active material, and coated active material for lithium-ion battery
CN105917499A (en) * 2014-01-16 2016-08-31 信越化学工业株式会社 Negative electrode material for nonaqueous electrolyte secondary batteries and method for producing negative electrode active material particles
CN105993088A (en) * 2014-03-12 2016-10-05 三洋化成工业株式会社 Coated negative-electrode active material for use in lithium-ion battery, slurry for use in lithium-ion battery, negative electrode for use in lithium-ion battery, lithium-ion battery, and method for manufacturing coated negative-electrode active material for use in lithium-ion battery
CN106129347A (en) * 2016-06-24 2016-11-16 深圳大学 Porous silicon composite negative pole material and preparation method thereof and lithium ion battery

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013047024A1 (en) * 2011-09-26 2013-04-04 日本電気株式会社 Lithium secondary battery and vehicle using same
US9139737B1 (en) * 2011-11-21 2015-09-22 Nanophase Technologies Corporation Multifunctional coated powders and high solids dispersions
EP2690689A1 (en) * 2012-07-25 2014-01-29 Umicore Low cost Si-based negative electrodes with enhanced cycling performance
CN103474666B (en) * 2013-07-23 2016-03-02 江苏华东锂电技术研究院有限公司 The preparation method of lithium ion battery anode active material
JP6181590B2 (en) * 2014-04-02 2017-08-16 信越化学工業株式会社 Anode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
KR101586816B1 (en) * 2015-06-15 2016-01-20 대주전자재료 주식회사 Negative active material for non-aqueous electrolyte rechargeable battery, the preparation method thereof, and rechargeable battery including the same
CN106252596B (en) 2016-08-05 2019-08-13 深圳市贝特瑞新能源材料股份有限公司 Soft carbon composite cathode material of silicon/carbon/graphite, preparation method and lithium ion battery
CN114242971A (en) 2017-12-13 2022-03-25 贝特瑞新材料集团股份有限公司 Modified composite material, preparation method thereof and lithium ion battery
CN108682824A (en) * 2018-05-31 2018-10-19 深圳市贝特瑞新能源材料股份有限公司 A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery
KR101999191B1 (en) 2019-03-15 2019-07-11 대주전자재료 주식회사 Silicon oxide composite for anode material of secondary battery and method for preparing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105359309A (en) * 2013-07-08 2016-02-24 三洋化成工业株式会社 Resin for coating lithium-ion-battery active material, resin composition for coating lithium-ion-battery active material, and coated active material for lithium-ion battery
CN105917499A (en) * 2014-01-16 2016-08-31 信越化学工业株式会社 Negative electrode material for nonaqueous electrolyte secondary batteries and method for producing negative electrode active material particles
CN105993088A (en) * 2014-03-12 2016-10-05 三洋化成工业株式会社 Coated negative-electrode active material for use in lithium-ion battery, slurry for use in lithium-ion battery, negative electrode for use in lithium-ion battery, lithium-ion battery, and method for manufacturing coated negative-electrode active material for use in lithium-ion battery
CN106129347A (en) * 2016-06-24 2016-11-16 深圳大学 Porous silicon composite negative pole material and preparation method thereof and lithium ion battery

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019227972A1 (en) * 2018-05-31 2019-12-05 深圳市贝特瑞新能源材料股份有限公司 Composite negative electrode material for lithium ion battery, preparation method therefor and use thereof in lithium ion battery
US11909035B2 (en) 2018-05-31 2024-02-20 Btr New Material Group Co., Ltd. Composite negative electrode material for lithium ion battery, preparation method thereof, and use thereof in lithium ion battery
CN109494360A (en) * 2018-10-26 2019-03-19 合肥国轩高科动力能源有限公司 A kind of oxidation Asia silicon composite and preparation method thereof
CN112968151A (en) * 2019-12-12 2021-06-15 郑州宇通集团有限公司 Negative electrode active material, preparation method thereof and lithium ion battery
CN112968151B (en) * 2019-12-12 2022-11-01 郑州宇通集团有限公司 Negative electrode active material, preparation method thereof and lithium ion battery
CN112259736A (en) * 2020-10-27 2021-01-22 成都新柯力化工科技有限公司 Lithium titanate negative electrode for relieving flatulence of lithium battery and preparation method
CN112574659A (en) * 2020-12-11 2021-03-30 中国科学院青岛生物能源与过程研究所 Electrode plate protective layer of lithium secondary battery and preparation method thereof

Also Published As

Publication number Publication date
KR102558278B1 (en) 2023-07-24
US20210159492A1 (en) 2021-05-27
KR20200142054A (en) 2020-12-21
WO2019227972A1 (en) 2019-12-05
US11909035B2 (en) 2024-02-20
EP3758114A4 (en) 2021-11-24
JP2021520050A (en) 2021-08-12
EP3758114A1 (en) 2020-12-30
JP7095176B2 (en) 2022-07-04

Similar Documents

Publication Publication Date Title
CN108682824A (en) A kind of composite negative electrode material of lithium ion battery, preparation method and the purposes in lithium ion battery
CN108054368B (en) Silicon-based negative electrode material, preparation method thereof and application thereof in lithium ion battery
CN103117414B (en) A kind of negative pole lithium titanate battery electrolyte, lithium ion battery and preparation method thereof
CN108550827B (en) Preparation method and application of three-dimensional porous silicon-carbon anode material
EP3041069B1 (en) Battery electrode paste composition
CN107248592A (en) A kind of novel high-power lithium ion battery with high energy density
CN106299377B (en) A kind of bonder for lithium ion batteries and the lithium ion battery using the binder
CN107749464A (en) A kind of energy density lithium ion power battery
KR20150063269A (en) Composite electrode for lithium air battery, preparing method thereof, and lithium air battery including the same
CN105702960A (en) Composite binder, lithium secondary battery positive electrode using composite binder, and making method of positive electrode
CN109686923A (en) The preparation method of pre- embedding cathode of lithium and pre- embedding cathode of lithium, energy storage device, energy-storage system and the electrical equipment being prepared
CN107316995A (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN109119694A (en) Lithium battery containing Multi-network
CN113644313A (en) Intrinsic stretchable double-network ionic gel electrolyte and preparation method and application thereof
CN106972151A (en) A kind of negative electrode of lithium ion battery composite pole piece and its lithium ion battery
CN104425796B (en) Manufacturing method, electrode and the electric energy storage device of electrode material
CN109904434A (en) A kind of porous lithium salts aeroge coated graphite composite material and preparation method
CN112457805B (en) Adhesive, preparation method thereof, silicon-carbon negative electrode material and lithium battery
CN109037658A (en) A kind of lithium iron phosphate positive material preparation method of polymer overmold
CN108017669B (en) Preparation method of phosphinate, phosphinate and nonaqueous electrolyte
CN108123139A (en) A kind of dedicated high temperature resistant binder of lithium battery and preparation method thereof
CN106898817A (en) Lithium-ion battery electrolytes and lithium ion battery
CN106207123B (en) A kind of aluminium ion battery sulphur/titanium dioxide/pyrolysis carbon composite anode material and preparation method thereof, aluminium ion battery
CN109473716A (en) Lithium ion battery polymer electrolyte film and preparation method thereof
US20230106786A1 (en) Silicon-based anode material, preparation method therefor and use thereof in lithium-ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Applicant after: Beitrei New Materials Group Co.,Ltd.

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Applicant before: Shenzhen BTR New Energy Materials Inc.

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20181019